1,2-Dichlorobenzene → HCID 42636428, compound

HRID 1092443Notes

Reaction equation

HRID 1092443 reaction equation
C([O:8][C@H:9]1[C@H:16]([O:17]CC2C=CC=CC=2)[C@@H:15]([O:25]CC2C=CC=CC=2)[C@H:14]([C:33]2[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]3[CH:46]=[CH:45][C:44]([CH2:47][CH3:48])=[CH:43][CH:42]=3)[CH:34]=2)[C:11]2([CH2:13][CH2:12]2)[C@@H:10]1[CH2:49][O:50]CC1C=CC=CC=1)C1C=CC=CC=1.ClC1C=CC=CC=1Cl.[H][H]>C1COCC1.CO.[Pd]>[Cl:39][C:36]1[CH:37]=[CH:38][C:33]([C@H:14]2[C@H:15]([OH:25])[C@@H:16]([OH:17])[C@H:9]([OH:8])[C@@H:10]([CH2:49][OH:50])[C:11]32[CH2:12][CH2:13]3)=[CH:34][C:35]=1[CH2:40][C:41]1[CH:42]=[CH:43][C:44]([CH2:47][CH3:48])=[CH:45][CH:46]=1

Participants

7

Reactant 3

HCID 72391,2-DichlorobenzeneHCID 66588531HCID 66588531, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 42636428HCID 42636428, compoundYield 37.3%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (4R,5R,6R,7S,8S)-5,6,7-tris(benzyloxy)-4-(benzyloxymethyl)-8-(4-chloro-3-(4-ethylbenzyl)phenyl)spiro[2.5]octane (36, 20 mg, 25.7 μmol) in a mixture of THF (0.2 mL) and methanol (0.8 mL) was added 1,2-dichlorobenzene (58 μL, 515 μmol) followed by 14 mg of palladium on charcoal (10%). The mixture was stirred under 1 atmosphere of hydrogen for 40 minutes. The mixture was filtered through a small pad of Celite in a 6 mL syringe and the Celite pad was washed with methanol (1 mL). Solvent was evaporated under reduced pressure and the residue was purified on preparative TLC plate (8:1 DCM:EtOH) to get 4 mg (37%) of compound 37 as a white solid. 1H NMR (300 MHz, CDCl3) δ 7.27-6.85 (m, 7H), 4.01 (s, 2H), 3.80 (m, 2H), 3.63 (m, H), 3.35 (d, J=5.1 Hz, 2H), 3.02 (d, J=11.1 hz, 1H), 2.62 (q, J=7.5 Hz, 2H), 2.06 (m, 1H), 1.21 (t, J=7.5 Hz, 3H), 0.40 (m, 1H), 0.29 (m, 1H), 0.076 (m, 1H), −0.326 (m, 1H). LC-ESI-MS m/z 418 (M+H), 440 (M+Na).

Workup

  1. filtrationThe mixture was filtered through a small pad of Celite in a 6 mL syringe
  2. washthe Celite pad was washed with methanol (1 mL)
  3. customSolvent was evaporated under reduced pressure
  4. customthe residue was purified on preparative TLC plate (8:1 DCM:EtOH)

Sources & evidence

ORD record
ord-8ba72ce37e5a4e7390add5ab045526c8
Source dataset
uspto-grants-2012_03
Patent number
US08129434B2

Reaction notes

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